Lithium-ion batteries with high-performance anodes comprising graphite(s) and silicon-based nanocomposites

Abstract

A battery anode includes a binder, a conductive additive, and an active material blend including silicon (Si)-comprising active material particles and graphite active material particles. In some embodiments, the battery anode has a reversible capacity loading in a range of about 2 mAh/cm 2 to about 16 mAh/cm 2 , the silicon (Si)-comprising active material particles exhibit a specific capacity in a range of about 800 mAh/g to about 3000 mAh/g, and the silicon (Si)-comprising active material particles contribute from about 25% to about 99% of a total capacity of the battery anode.

1 . A battery anode, comprising:
 a binder;   a conductive additive; and   an active material blend comprising silicon (Si)-comprising active material particles and graphite active material particles,   wherein:   the battery anode has a reversible capacity loading in a range of about 2 mAh/cm 2  to about 16 mAh/cm 2 ;   the Si-comprising active material particles exhibit a specific capacity in a range of about 800 mAh/g to about 3000 mAh/g;   the Si-comprising active material particles contribute from about 25% to about 99% of a total capacity of the battery anode; and   at least a subset of the graphite active material particles is characterized by a Raman spectrum in which a full-width half-maximum (FWHM) of a D band is in a range of about 30 cm −1  to about 90 cm 1 , a FWHM of a G band is in a range from about 5 cm −1  to about 105 cm 1 , a FWHM of a 2D 1  band is in a range from about 30 cm −1  to about 110 cm −1 , and a D/G peak intensity ratio, defined as an intensity of a D peak divided by an intensity of a G peak, is in a range from about 0.02 to about 1.12.   
     
     
         2 . The battery anode of  claim 1 , wherein the D/G peak intensity ratio is in a range from about 0.12 to about 0.30. 
     
     
         3 . The battery anode of  claim 1 , wherein:
 a 2D 1 /G peak intensity ratio, defined as an intensity of a 2D 1  peak of the Raman spectrum divided by the intensity of the G peak, is in a range from about 0.10 to about 0.90.   
     
     
         4 . The battery anode of  claim 1 , wherein:
 the at least the subset of the graphite active material particles is characterized by an X-ray diffraction (XRD) spectrum in which a FWHM of a (002) reflection peak is within a range from about 0.220 degrees to about 5.620 degrees.   
     
     
         5 . The battery anode of  claim 4 , wherein the FWHM of the (002) reflection peak is within a range from about 0.220 degrees to about 0.620 degrees. 
     
     
         6 . The battery anode of  claim 4 , wherein:
 an average crystallite size of the at least the subset of the graphite active material particles as estimated by applying the Scherrer formula to the (002) reflection peak is in a range of about 1 nm to about 40 nm.   
     
     
         7 . The battery anode of  claim 6 , wherein the average crystallite size is within a range of about 15 nm to about 30 nm. 
     
     
         8 . The battery anode of  claim 1 , wherein:
 an average pressure (Cx) required to deform the at least the subset of the graphite active material particles by 10% during a micro-compression hardness test ranges from about 1 MPa to about 30 MPa.   
     
     
         9 . The battery anode of  claim 8 , wherein:
 the average pressure ranges from about 1 MPa to about 18 MPa.   
     
     
         10 . The battery anode of  claim 1 , wherein:
 a tap density of the at least the subset of the graphite active material particles ranges from about 0.10 g/cc to about 1.25 g/cc.   
     
     
         11 . The battery anode of  claim 10 , wherein:
 the tap density ranges from about 0.90 g/cc to about 1.10 g/cc.   
     
     
         12 . The battery anode of  claim 1 , wherein:
 a pycnometry density of the at least the subset of the graphite active material particles ranges from about 2.15 g/cc to about 2.35 g/cc.   
     
     
         13 . The battery anode of  claim 1 , wherein:
 a fiftieth-percentile volume-weighted particle size parameter (D 50 ) of the at least the subset of the graphite active material particles ranges from about 2 m to about 22 m.   
     
     
         14 . The battery anode of  claim 13 , wherein:
 the D 50  ranges from about 12 m to about 17 m.   
     
     
         15 . The battery anode of  claim 1 , wherein:
 a ninetieth-percentile volume-weighted particle size parameter (D 90 ) of the at least the subset of the graphite active material particles ranges from about 4 m to about 30 m.   
     
     
         16 . The battery anode of  claim 15 , wherein:
 the D 90  ranges from about 19 μm to about 26 m.   
     
     
         17 . The battery anode of  claim 1 , wherein:
 a tenth-percentile volume-weighted particle size parameter (D 10 ) of the at least the subset of the graphite active material particles ranges from about 0.5 m to about 15 m.   
     
     
         18 . The battery anode of  claim 17 , wherein:
 the D 10  ranges from about 7 m to about 11 m.   
     
     
         19 . The battery anode of  claim 1 , wherein:
 a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the at least the subset of the graphite active material particles ranges from about 0.450 m 2 /g to about 450 m 2 /g.   
     
     
         20 . The battery anode of  claim 19 , wherein:
 the BET-SSA ranges from about 1 m 2 /g to about 5 m 2 /g.   
     
     
         21 . The battery anode of  claim 1 , wherein:
 a weight fraction of the at least the subset of the graphite active material particles in the battery anode is in a range of about 1 wt. % to about 50 wt. % of the active material blend.   
     
     
         22 . The battery anode of  claim 21 , wherein:
 the weight fraction is in a range of about 2 wt. % to about 20 wt. % of the active material blend.   
     
     
         23 . The battery anode of  claim 1 , wherein:
 the Si-comprising active material particles comprise oxygen (O) atoms at about 5 wt. % or less of a total mass of the Si-comprising active material particles.   
     
     
         24 . The battery anode of  claim 1 , wherein:
 the Si-comprising active material particles comprise silicon (Si) atoms and carbon (C) atoms, in aggregate, in a range of 80 wt. % to about 100 wt. % of a total mass of the Si-comprising active material particles.   
     
     
         25 . The battery anode of  claim 24 , wherein:
 the Si-comprising active material particles comprise Si—C nanocomposite particles.   
     
     
         26 . The battery anode of  claim 1 , wherein:
 the at least the subset of the graphite active material particles exhibits a specific capacity in a range of about 320 mAh/g to about 372 mAh/g.   
     
     
         27 . A lithium-ion battery, comprising:
 the battery anode of  claim 1 ;   a cathode;   a separator electrically separating the battery anode and the cathode; and   an electrolyte ionically coupling the battery anode and the cathode.   
     
     
         28 . A battery anode, comprising:
 a binder;   a conductive additive; and   an active material blend comprising silicon (Si)-comprising active material particles and graphite active material particles,   wherein:   a mass fraction of the Si in the Si-comprising active material particles is in a range of about 20 wt. % to about 80 wt. %;   a mass ratio of the Si-comprising active material particles to the graphite active material particles is in a range of about 60:40 to about 98:2;   at least a subset of the graphite active material particles is characterized by a Raman spectrum in which a full-width half-maximum (FWHM) of a D band is in a range of about 30 cm −1  to about 90 cm −1 , a FWHM of a G band is in a range from about 5 cm −1  to about 105 cm −1 , a FWHM of a 2D 1  band is in a range from about 30 cm −1  to about 110 cm −1 , and a D/G peak intensity ratio, defined as an intensity of a D peak divided by an intensity of a G peak, is in a range from about 0.02 to about 1.12; and   an average pressure (Cx) required to deform the at least the subset of the graphite active material particles by 10% during a micro-compression hardness test ranges from about 1 MPa to about 18 MPa.   
     
     
         29 . The battery anode of  claim 28 , wherein:
 the mass ratio of the Si-comprising active material particles to the graphite active material particles is in a range of about 75:25 to about 95:5.   
     
     
         30 . The battery anode of  claim 28 , wherein:
 the average pressure ranges from about 7 MPa to about 18 MPa.   
     
     
         31 . The battery anode of  claim 30 , wherein:
 the average pressure ranges from about 10 MPa to about 18 MPa.   
     
     
         32 . The battery anode of  claim 28 , wherein the D/G peak intensity ratio is in a range from about 0.12 to about 0.30. 
     
     
         33 . The battery anode of  claim 28 , wherein:
 a tap density of the at least the subset of the graphite active material particles ranges from about 0.10 g/cc to about 1.25 g/cc.   
     
     
         34 . The battery anode of  claim 33 , wherein:
 the tap density ranges from about 0.90 g/cc to about 1.10 g/cc.   
     
     
         35 . The battery anode of  claim 28 , wherein:
 a fiftieth-percentile volume-weighted particle size parameter (D 50 ) of the at least the subset of the graphite active material particles ranges from about 2 m to about 22 m.   
     
     
         36 . The battery anode of  claim 35 , wherein:
 the D 50  ranges from about 11 m to about 17 m.   
     
     
         37 . The battery anode of  claim 36 , wherein:
 the D 50  ranges from about 12 m to about 17 m.   
     
     
         38 . The battery anode of  claim 28 , wherein:
 a ninetieth-percentile volume-weighted particle size parameter (D 90 ) of the at least the subset of the graphite active material particles ranges from about 4 m to about 30 m.   
     
     
         39 . The battery anode of  claim 38 , wherein:
 the D 90  ranges from about 19 μm to about 30 am.   
     
     
         40 . The battery anode of  claim 39 , wherein:
 the D 90  ranges from about 19 μm to about 26 am.   
     
     
         41 . The battery anode of  claim 28 , wherein:
 a tenth-percentile volume-weighted particle size parameter (D 10 ) of the at least the subset of the graphite active material particles ranges from about 0.5 m to about 15 am.   
     
     
         42 . The battery anode of  claim 41 , wherein:
 the D 10  ranges from about 5 m to about 11 m.   
     
     
         43 . The battery anode of  claim 42 , wherein:
 the D 10  ranges from about 7 m to about 11 m.   
     
     
         44 . The battery anode of  claim 28 , wherein:
 a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the at least the subset of the graphite active material particles ranges from about 0.450 m 2 /g to about 450 m 2 /g.   
     
     
         45 . The battery anode of  claim 44 , wherein:
 the BET-SSA ranges from about 1 m 2 /g to about 5 m 2 /g.   
     
     
         46 . The battery anode of  claim 45 , wherein:
 the BET-SSA ranges from about 1 m 2 /g to about 3 m 2 /g.   
     
     
         47 . The battery anode of  claim 28 , wherein:
 the Si-comprising active material particles comprise oxygen (O) atoms at about 5 wt. % or less of a total mass of the Si-comprising active material particles.   
     
     
         48 . The battery anode of  claim 28 , wherein:
 the Si-comprising active material particles comprise silicon (Si) atoms and carbon (C) atoms, in aggregate, in a range of about 80 wt. % to about 100 wt. % of a total mass of the Si-comprising active material particles.   
     
     
         49 . The battery anode of  claim 48 , wherein:
 the Si-comprising active material particles comprise Si—C nanocomposite particles.   
     
     
         50 . The battery anode of  claim 28 , wherein:
 the at least the subset of the graphite active material particles exhibits a specific capacity in a range of about 320 mAh/g to about 372 mAh/g.   
     
     
         51 . The battery anode of  claim 28 , wherein:
 the battery anode has a reversible capacity loading in a range of about 2 mAh/cm 2  to about 16 mAh/cm 2 .   
     
     
         52 . A lithium-ion battery, comprising:
 the battery anode of  claim 28 ;   a cathode;   a separator electrically separating the battery anode and the cathode; and   an electrolyte ionically coupling the battery anode and the cathode.   
     
     
         53 . A battery anode, comprising:
 a binder;   a conductive additive; and   an active material blend comprising silicon (Si)-comprising active material particles and graphite active material particles,   wherein:   a mass fraction of the Si in the Si-comprising active material particles is in a range of about 20 wt. % to about 80 wt. %;   a mass ratio of the Si-comprising active material particles to the graphite active material particles is in a range of about 7:93 to about 40:60;   at least a subset of the graphite active material particles is characterized by a Raman spectrum in which a full-width half-maximum (FWHM) of a D band is in a range of about 30 cm −1  to about 90 cm −1 , a FWHM of a G band is in a range from about 5 cm −1  to about 105 cm −1 , a FWHM of a 2D 1  band is in a range from about 30 cm −1  to about 110 cm −1 , and a D/G peak intensity ratio, defined as an intensity of a D peak divided by an intensity of a G peak, is in a range from about 0.02 to about 1.12; and   an average pressure (Cx) required to deform the at least the subset of the graphite active material particles by 10% during a micro-compression hardness test ranges from about 20 MPa to about 30 MPa.   
     
     
         54 . The battery anode of  claim 53 , wherein:
 the mass ratio of the Si-comprising active material particles to the graphite active material particles is in a range of about 10:90 to about 30:70.   
     
     
         55 . The battery anode of  claim 53 , wherein:
 the average pressure ranges from about 24 MPa to about 30 MPa.   
     
     
         56 . The battery anode of  claim 53 , wherein the D/G peak intensity ratio is in a range from about 0.08 to about 0.30. 
     
     
         57 . The battery anode of  claim 53 , wherein:
 a tap density of the at least the subset of the graphite active material particles ranges from about 0.10 g/cc to about 1.25 g/cc.   
     
     
         58 . The battery anode of  claim 57 , wherein:
 the tap density ranges from about 0.90 g/cc to about 1.20 g/cc.   
     
     
         59 . The battery anode of  claim 58 , wherein:
 the tap density ranges from about 0.90 g/cc to about 1.10 g/cc.   
     
     
         60 . The battery anode of  claim 53 , wherein:
 a fiftieth-percentile volume-weighted particle size parameter (D 50 ) of the at least the subset of the graphite active material particles ranges from about 2 m to about 22 m.   
     
     
         61 . The battery anode of  claim 60 , wherein:
 the D 50  ranges from about 11 m to about 17 m.   
     
     
         62 . The battery anode of  claim 61 , wherein:
 the D 50  ranges from about 12 m to about 17 m.   
     
     
         63 . The battery anode of  claim 53 , wherein:
 a ninetieth-percentile volume-weighted particle size parameter (D 90 ) of the at least the subset of the graphite active material particles ranges from about 4 m to about 30 μm.   
     
     
         64 . The battery anode of  claim 63 , wherein:
 the D 90  ranges from about 19 μm to about 30 m.   
     
     
         65 . The battery anode of  claim 53 , wherein:
 a tenth-percentile volume-weighted particle size parameter (D 10 ) of the at least the subset of the graphite active material particles ranges from about 0.5 m to about 15 m.   
     
     
         66 . The battery anode of  claim 65 , wherein:
 the D 10  ranges from about 5 m to about 11 m.   
     
     
         67 . The battery anode of  claim 53 , wherein:
 a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the at least the subset of the graphite active material particles ranges from about 0.450 m 2 /g to about 450 m 2 /g.   
     
     
         68 . The battery anode of  claim 67 , wherein:
 the BET-SSA ranges from about 1 m 2 /g to about 5 m 2 /g.   
     
     
         69 . The battery anode of  claim 68 , wherein:
 the BET-SSA ranges from about 1 m 2 /g to about 3 m 2 /g.   
     
     
         70 . The battery anode of  claim 53 , wherein:
 the Si-comprising active material particles comprise oxygen (O) atoms at about 5 wt. % or less of a total mass of the Si-comprising active material particles.   
     
     
         71 . The battery anode of  claim 53 , wherein:
 The Si-comprising active material particles comprise silicon (Si) atoms and carbon (C) atoms, in aggregate, in a range of about 80 wt. % to about 100 wt. % of a total mass of the Si-comprising active material particles.   
     
     
         72 . The battery anode of  claim 71 , wherein:
 the Si-comprising active material particles comprise Si—C nanocomposite particles.   
     
     
         73 . The battery anode of  claim 53 , wherein:
 the at least the subset of the graphite active material particles exhibits a specific capacity in a range of about 320 mAh/g to about 372 mAh/g.   
     
     
         74 . The battery anode of  claim 53 , wherein:
 the battery anode has a reversible capacity loading in a range of about 2 mAh/cm 2  to about 16 mAh/cm 2 .   
     
     
         75 . A lithium-ion battery, comprising:
 the battery anode of  claim 53 ;   a cathode;   a separator electrically separating the battery anode and the cathode; and   an electrolyte ionically coupling the battery anode and the cathode.